Electroluminescence device, cyclic azine compound and production process of cyclic azine dye

ABSTRACT

An organic electroluminescence device including at least one organic thin film between electrodes, which contains at least one compound represented by the following formula (1):                    
     wherein X 11  represents a sulfur atom or N—R 19 , and R 11  to R 18  and R 19 , which may be the same or different, each represents a hydrogen atom or a substituent, provided that R 16  and R 17  are not combined to form an aromatic ring.

This is a divisional of application Ser. No. 09/179,837 filed Oct. 28,1998, now U.S. Pat. No. 6,379,823; the disclosure of which isincorporated herein by reference.

FIELD OF THE INVENTION

The present invention relates to a cyclic azine dye and anelectroluminescence (EL) device using the same.

BACKGROUND OF THE INVENTION

At the present time, development and study on various display devicesare aggressively driven. In particular, organic EL devices can obtainhigh luminance light emission at a low voltage and accordingly, aredrawing an attention as a promising display device. For example, an ELdevice comprising an organic thin film formed by depositing an organiccompound is known (see, Applied Physics Letters, Vol. 51, page 913(1987)). The organic EL device described in this publication has alaminate structure comprising an electron transporting material and ahole transporting material and is greatly improved in the light emissionproperties as compared with conventional single-layer devices.

As a means to improve the light emission efficiency of the laminate-typeEL device, a method of doping a fluorescent dye is known. For example,an organic EL device having doped therein a coumarin dye described inJournal of Applied Physics, Vol. 65, page 3,610 (1989) is greatlyimproved in the light emission efficiency as compared with non-dopeddevices.

Furthermore, by doping a fluorescent dye, light having a desiredwavelength can be taken out. In order to apply the organic EL device toa full color display or back light, a fluorescent dye capable ofemitting light at an appropriate wavelength and having excellentdurability must be developed, in particular, a red fluorescent dye isbeing demanded in view of durability and light emission efficiency.

As the red fluorescent dye used in the organic electroluminescencedevice,4-(dicyanomethylene)-2-methyl-6-(4-dimethylaminostyryl)-4H-pyrane (DCM),for example, is doped and thereby emission of red orange light isobtained, however, this dye has problems that the color purity is lowand the durability is poor, and cannot be used in practice. Neil Red isalso known, however, this is still disadvantageous in that the color hueis short wave and the durability is not sufficiently high. In the sameway, various EL devices which can emit light at a longer wavelength thanthe green light as a result of doping a fluorescent material have beendeveloped, however, these devices all have serious problems that thecolor purity is low as red color light emission and the luminance ofemitted light is not sufficiently high. EL devices using a conventionalred fluorescent dye have another problem that the durability is low.Furthermore, with respect to a fluorescent dye which emits light in theblue green area, dyes capable of emitting light with excellent luminanceand having superior durability have not yet been developed and a new dyeis being demanded.

Of organic EL devices, devices in which an organic material is laminatedby vacuum deposition can successfully achieve high luminance lightemission, however, in view of simplification of the production process,workability and the like or for obtaining a large area, the device ispreferably fabricated by a coating method. The devices fabricated by theconventional coating method are, however, inferior in the luminance ofemitted light and the light emission efficiency to the devicesfabricated by the deposition method. Thus, improvements are still inneed for attaining high luminance and highly efficient light emission.

SUMMARY OF THE INVENTION

A first object of the present invention is to provide an organic ELdevice using a red fluorescent dye capable of emitting red light in highcolor purity and having excellent durability.

A second object of the present invention is to provide a red fluorescentdye which can be used in an organic EL device, emits red light in highcolor purity and has excellent durability.

A third object of the present invention is to provide an organic ELdevice which can ensure high luminance and highly efficient lightemission even when the device is fabricated by a coating method.

A fourth object of the present invention is to provide an organic ELdevice using a fluorescent dye capable of emitting light in the bluegreen area and having excellent durability.

The present invention provides the following electroluminescence devicesand fluorescent dyes and thereby the above-described objects of thepresent invention can be attained.

[1] An organic electroluminescence device comprising at least oneorganic thin film between electrodes, which contains at least onecompound represented by the following formula (1), (2) or (3):

wherein X₁₁ represents an oxygen atom, a sulfur atom or N—R₁₉, and R₁₁to R₁₈ and R₁₉, which may be the same or different, each represents ahydrogen atom or a substituent, provided that R₁₆ and R₁₇ are notcombined to form an aromatic ring;

wherein X₂₁ represents an oxygen atom, a sulfur atom or N—R_(2b), Y₂₁represents an oxygen atom or a sulfur atom, and R₂₁ to R₂₉ and R_(2b),which may be the same or different, each represents a hydrogen atom or asubstituent, and R_(2a) represents a hydrogen atom, an alkyl group, analkenyl group, an alkynyl group, an aryl group, a heterocyclic group, anunsubstituted amino group, an acylamino group, a sulfonyl-amino group, acarbamoylamino group, a sulfamoylamino group, an alkoxycarbonylaminogroup, an aryloxycarbonylamino group, a phosphoramido group, an acylgroup, a carbamoyl group, a sulfonyl group, a sulfamoyl group, a cyanogroup or a halogen atom, provided that when X₂₁ represents an oxygenatom and R₂₉ represents a hydrogen atom, at least one of R₂₆ to R₂₉represents an unsubstituted or substituted amino group;

wherein X₃₁, represents an oxygen atom, a sulfur atom or N—R_(3b), Z₃₁,represents NR₃₁R₃₂ or OG₃₁, R₃₁ to R₃₆ and R_(3b) each represents ahydrogen atom or a substituent, and G₃₁ represents a hydrogen atom, asubstituent or a counter cation group.

[2] A cyclic azine compound having a structure represented by thefollowing formula (4):

wherein X₄₁ represents an oxygen atom, a sulfur atom or N—R_(4b), R_(4b)represents a hydrogen atom, a substituted or unsubstituted alkyl grouphaving from 1 to 20 carbon atoms, a substituted carbonyl group havingfrom 1 to 20 carbon atoms or a substituted sulfonyl group having from 0to 20 carbon atoms, R₄, and R₄₂ each represents a substituted orunsubstituted alkyl group having from 1 to 20 carbon atoms or an arylgroup having from 6 to 20 carbon atoms, R₄₃, R₄₄ and R₄₅ each representsa hydrogen atom, a substituted or unsubstituted alkyl group having from1 to 20 carbon atoms, a halogen atom, a hydroxy group, a substituted orunsubstituted alkoxy group having from 1 to 20 carbon atoms, anunsubstituted amino group, a substituted amino group having from 1 to 20carbon atoms, the substituted amino group being an alkylamino group, anarylamino group, a sulfonamido group, a carbonamido group, a ureidogroup, a urethane group, a carbamoylamino group or a sulfamoylaminogroup, R₄₆, R₄₇, R₄₈ and R₄₉ each represents a hydrogen atom, a halogenatom, a substituted carbonyl group having from 1 to 30 carbon atoms, analkylamino group having from 1 to 30 carbon atoms, an arylamino grouphaving from 6 to 30 carbon atoms a sulfonylamino group having from 1 to30 carbon atoms, an acylamino group having from 2 to 30 carbon atoms, aureido group having from 1 to 30 carbon atoms, an alkoxycarbonylaminogroup having from 2 to 30 carbon atoms, an aryloxycarbonylamino grouphaving from 7 to 30 carbon atoms, a carbamoylamino group having from 1to 30 carbon atoms or a sulfamoylamino group having from 1 to 30 carbonatoms, and R_(4a) represents a hydrogen atom, a cyano group, asubstituted carbonyl group having from 1 to 30 carbon atoms, a sulfamoylgroup having from 0 to 30 carbon atoms, a sulfonyl group having from 1to 30 carbon atoms, a sulfonamido group having from 1 to 30 carbonatoms, a carbonamido group having from 1 to 30 carbon atoms or a ureidogroup having from 1 to 30 carbon atoms, provided that when X₄₁ is anoxygen atom and R_(4a), represents a hydrogen atom or a cyano group, atleast one of R₄₆ to R₄₉ represents a substituted amino group and whenX₄₁ represents a sulfur atom, R_(4a) represents a hydrogen atom, a cyanogroup or a sulfamoyl group, the substituent of the substituted carbonylgroup being an alkyl group, an aryl group, a heterocyclic group, analkoxy group, an aryloxy group, an arylamino group or an alkylaminogroup.

[3] An organic electroluminescence device comprising a pair ofelectrodes having formed therebetween a light emitting layer or aplurality of organic compound thin films including a light emittinglayer, wherein at least one layer is a layer comprising a polymer havingdispersed therein a compound represented by formula (1), (2), (3) or (4)described in the above items [1] and [2].

[4] An organic electroluminescence device comprising a pair ofelectrodes having formed therebetween a light emitting layer or aplurality of organic compound thin film including a light emittinglayer, wherein at least one layer is a layer formed by coating acompound represented by formula (1), (2), (3) or (4) described in theabove items [1] and [2] or a material containing the compound.

[5] A process for producing a cyclic azine dye represented by thefollowing formula (15), comprising reacting a phenylenediaminederivative represented by the following formula (13) with a phenolderivative represented by the following formula (14) in the presence ofan oxidizing agent in an alkaline atmosphere:

wherein X₁₃₁, represents an oxygen atom, a sulfur atom or N—R₁₃₉, R₁₃₁to R₁₃₅ and R₁₃₉, which may be the same or different, each represents ahydrogen atom or a substituent, R₁₃₆ to R₁₃₈, which may be the same ordifferent, each represents a hydrogen atom or a substituent, and Y₁₃₁ toY₁₃₄, which may be the same or different, each represents a hydrogenatom or a splitting-off group.

[6] A process for producing a cyclic azine dye represented by thefollowing formula (18), comprising oxidation reacting an anilinederivative represented by formula (16) or (17) by an oxidizing agent inan alkaline atmosphere:

wherein X₁₆₁ represents an oxygen atom, a sulfur atom or N—R₁₆₉, R₁₆₁ toR₁₆₈ and R₁₆₉, which may be the same or different, each represents ahydrogen atom or a substituent, X₁₇₁ represents an oxygen atom, a sulfuratom or N—R₁₇₉, R₁₇₁ to R₁₇₈ and R₁₇₉, which may be the same ordifferent each represents a hydrogen atom or a substituent, and Y₁₆₁ toY₁₆₃ and Y₁₇₁ to Y₁₇₃, which may be the same or different, eachrepresents a hydrogen atom or a splitting-off group.

[7] A process for producing a cyclic azine dye represented by formula(3), comprising reacting a carbonyl compound derivative represented bythe following formula (19) with an aniline compound derivativerepresented by the following formula (20) or a salt thereof in thepresence of an oxidizing agent in an alkaline atmosphere:

wherein X₂₀₁ represents an oxygen atom, a sulfur atom or >NR₁₉₂, R₁₉₂represents a hydrogen atom or a substituent, R₁₉₁ represents a hydrogenatom or a substituent, Y₁₉₁ and Y₁₉₂, which may be the same ordifferent, each represents a hydrogen atom or a splitting-off group,Z₁₉₁ represents —NR₁₉₃R₁₉₄ or —OG₁₉₁, R₁₉₃ and R₁₉₄, which may be thesame or different, each represents a hydrogen atom or a substituent,G₁₉₁ represents a hydrogen atom, a substituent or a counter cationgroup, R₁₉₅ represents a substituent, and n³ represents 0 or an integerof from 1 to 3, provided that when n³ is 2 or 3, the plurality of R₁₉₅groups may be the same or different.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is described in detail below.

Formula (1) is described below. X₁₁ represents an oxygen atom, a sulfuratom or N—R₁₉, preferably an oxygen atom or N—R₁₉. R₁₉ represents ahydrogen atom or a substituent.

Examples of the substituent include an alkyl group preferably havingfrom 1 to 20 carbon atoms, more preferably from 1 to 12 carbon atoms,still more preferably from 1 to 8 carbon atoms, such as methyl, ethyl,iso-propyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl,cyclopentyl and cyclohexyl; an alkenyl group preferably having from 2 to20 carbon atoms, more preferably from 2 to 12 carbon atoms, still morepreferably from 2 to 8 carbon atoms, such as vinyl, allyl, 2-butenyl and3-pentenyl; an alkynyl group preferably having from 2 to 20 carbonatoms, more preferably from 2 to 12 carbon atoms, still more preferablyfrom 2 to 8 carbon atoms, such as propargyl and 3-pentynyl; an arylgroup preferably having from 6 to 30 carbon atoms, more preferably from6 to 20 carbon atoms, still more preferably from 6 to 12 carbon atoms,such as phenyl, p-methylphenyl and naphthyl; an acyl group preferablyhaving from 1 to 20 carbon atoms, more preferably from 1 to 16 carbonatoms, still more preferably from 1 to 12 carbon atoms, such as acetyl,benzoyl, formyl and pivaloyl; an alkoxycarbonyl group preferably havingfrom 2 to 20 carbon atoms, more preferably from 2 to 16 carbon atoms,still more preferably from 2 to 12 carbon atoms, such as methoxycarbonyland ethoxycarbonyl; an aryloxycarbonyl group preferably having from 7 to20 carbon atoms, more preferably from 7 to 16 carbon atoms, still morepreferably from 7 to 10 carbon atoms, such as phenyloxycarbonyl; analkylaminocarbonyl group preferably having from 1 to 40 carbon atoms,more preferably from 1 to 30 carbon atoms, still more preferably from 1to 25 carbon atoms, such as ethylaminocarbonyl anddimethylaminocarbonyl; an arylaminocarbonyl group preferably having from7 to 40 carbon atoms, more preferably from 7 to 30 carbon atoms, stillmore preferably from 7 to 10 carbon atoms, such as phenylaminocarbonyl;a sulfonyl group preferably having from 1 to 20 carbon atoms, morepreferably from 1 to 16 carbon atoms, still more preferably from 1 to 12carbon atoms, such as mesyl and tosyl; and a heterocyclic group,preferably a heterocyclic group having a 5- or 6-membered monocyclic orcondensed ring structure and having from 3 to 30 carbon atoms (thehetero atom is, for example, oxygen, nitrogen or sulfur), such asimidazolyl, pyridyl, furyl, piperidyl and morpholino.

These substituents each may further be substituted.

R₁₉ may be combined with R₁₃ or R₁₈ to form a 5- or 6-memberednitrogen-containing heterocyclic ring having from 3 to 20 carbon atoms.

R₁₉ is preferably a hydrogen atom, a substituted or unsubstituted alkylgroup having from 1 to 20 carbon atoms, a substituted carbonyl grouphaving from 1 to 20 carbon atoms or a substituted sulfonyl group havingfrom 1 to 20 carbon atoms. The substituent of the substituted carbonylgroup is an aliphatic group, an aryl group, a heterocyclic group, analkoxy group, an aryloxy group, a heterocyclic oxy group, anunsubstituted or substituted amino group or a hydroxyl group. Thesubstituent of the substituted sulfonyl group is an aliphatic group, anaryl group, an alkoxy group, a substituted or unsubstituted amino groupor a hydroxyl group. The substituted amino group is an alkylamino group,an arylamino group, a sulfonamido group, a carbonamido group, a ureidogroup, a urethane group, a carbamoylamino group or a sulfamoylaminogroup. R₁₉ is particularly preferably a hydrogen atom or an alkyl grouphaving from 1 to 10 carbon atoms.

R₁₁ to R₁₈, which may be the same or different, each represents ahydrogen atom or a substituent.

Examples of the substituents of R₁₁ and R₁₂ include the substituentsdescribed above for R₁₉.

Examples of the substituent of R₁₃ to R₁₈ include an alkyl group(preferably having from 1 to 30 carbon atoms, more preferably from 1 to20 carbon atoms, still more preferably from 1 to 12 carbon atoms, e.g.,methyl, ethyl, iso-propyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl,cyclopropyl, 2-ethylhexyl, cyclopentyl, cyclohexyl, trifluoromethyl,pentafluoromethyl), an alkenyl group (preferably having from 2 to 30carbon atoms, more preferably from 2 to 20 carbon atoms, still morepreferably from 2 to 12 carbon atoms, e.g., vinyl, allyl, 2-butenyl,3-pentenyl), an alkynyl group (preferably having from 2 to 30 carbonatoms, more preferably from 2 to 20 carbon atoms, still more preferablyfrom 2 to 12 carbon atoms, e.g., propargyl, 3-pentynyl), an aryl group(preferably having from 6 to 30 carbon atoms, more preferably from 6 to20 carbon atoms, still more preferably from 6 to 12 carbon atoms, e.g.,phenyl, p-methylphenyl, naphthyl, pentafluorophenyl), an unsubstitutedamino group, an alkyl-substituted or aryl-substituted amino group(preferably having from 1 to 30 carbon atoms, more preferably from 1 to20 carbon atoms, still more preferably from 1 to 12 carbon atoms, e.g.,amino, methylamino, dimethylamino, diethylamino, dibenzylamino,anilino), an alkoxy group (preferably having from 1 to 30 carbon atoms,more preferably from 1 to 20 carbon atoms, still more preferably from 1to 12 carbon atoms, e.g., methoxy, ethoxy, butoxy), an aryloxy group(preferably having from 6 to 30 carbon atoms, more preferably from 6 to20 carbon atoms, still more preferably from 6 to 12 carbon atoms, e.g.,phenyloxy, 2-naphthyloxy), an acyl group (preferably having from 1 to 30carbon atoms, more preferably from 1 to 20 carbon atoms, still morepreferably from 1 to 12 carbon atoms, e.g., acetyl, benzoyl, formyl,pivaloyl), an alkoxycarbonyl group (preferably having from 2 to 30carbon atoms, more preferably from 2 to 20 carbon atoms, still morepreferably from 2 to 12 carbon atoms, e.g., methoxycarbonyl,ethoxycarbonyl), an aryloxycarbonyl group (preferably having from 7 to30 carbon atoms, more preferably from 7 to 20 carbon atoms, still morepreferably from 7 to 12 carbon atoms, e.g., phenyloxycarbonyl), analkylaminocarbonyl group (preferably having from 2 to 40 carbon atoms,more preferably from 2 to 30 carbon atoms, still more preferably from 2to 25 carbon atoms, e.g., ethylaminocarbonyl, dimethylaminocarbonyl), anarylaminocarbonyl group (preferably having from 7 to 40 carbon atoms,more preferably from 7 to 30 carbon atoms, still more preferably from 7to 12 carbon atoms, e.g., phenylaminocarbonyl), an acyloxy group(preferably having from 2 to 30 carbon atoms, more preferably from 2 to20 carbon atoms, still more preferably from 2 to 12 carbon atoms, e.g.,acetoxy, benzoyloxy), an acylamino group (preferably having from 2 to 30carbon atoms, more preferably from 2 to 20 carbon atoms, still morepreferably from 2 to 12 carbon atoms, e.g., acetylamino, benzoylamino),an alkoxycarbonylamino group (preferably having from 2 to 30 carbonatoms, more preferably from 2 to 20 carbon atoms, still more preferablyfrom 2 to 12 carbon atoms, e.g., methoxycarbonylamino), anaryloxycarbonylamino group (preferably having from 7 to 30 carbon atoms,more preferably from 7 to 20 carbon atoms, still more preferably from 7to 12 carbon atoms, e.g., phenyloxycarbonylamino), a sulfonylamino group(preferably having from 1 to 30 carbon atoms, more preferably from 1 to20 carbon atoms, still more preferably from 1 to 12 carbon toms, e.g.,methane-sulfonylamino, benzenesulfonylamino), a sulfamoyl group(preferably having from 0 to 30 carbon atoms, more preferably from 0 to20 carbon atoms, still more preferably from 0 to 12 carbon atoms, e.g.,sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, phenylsulfamoyl), acarbamoyl group (preferably having from 1 to 30 carbon atoms, morepreferably from 1 to 20 carbon atoms, still more preferably from 1 to 12carbon atoms, e.g., carbamoyl, methylcarbamoyl, diethylcarbamoyl,phenylcarbamoyl), a carbamoylamino group (preferably having from 1 to 30carbon atoms, more preferably from 1 to 20 carbon atoms, still morepreferably from 1 to 12 carbon atoms, e.g., carbamoylamino,ethylcarbamoylamino, dimethylcarbamoylamino, phenylcarbamoylamino), asulfamoylamino group (preferably having from 0 to 30 carbon atoms, morepreferably from 0 to 20 carbon atoms, still more preferably from 0 to 12carbon atoms, e.g., sulfamoylamino, methylsulfamoylamino,diethylsulfamoylamino, phenylsulfamoylamino), an alkylthio group(preferably having from 1 to 30 carbon atoms, more preferably from 1 to20 carbon atoms, still more preferably from 1 to 12 carbon atoms, e.g.,methylthio, ethylthio), an arylthio group (preferably having from 6 to30 carbon atoms, more preferably from 6 to 20 carbon atoms, still morepreferably from 6 to 12 carbon atoms, e.g., phenylthio), a sulfonylgroup (preferably having from 1 to 30 carbon atoms, more preferably from1 to 20 carbon atoms, still more preferably from 1 to 12 carbon atoms,e.g., mesyl, tosyl), a sulfinyl group (preferably having from 1 to 30carbon atoms, more preferably from 1 to 20 carbon atoms, still morepreferably from 1 to 12 carbon atoms, e.g., methanesulfinyl,benzenesulfinyl), a ureido group (preferably having from 1 to 30 carbonatoms, more preferably from 1 to 20 carbon atoms, still more preferablyfrom 1 to 12 carbon atoms, e.g., ureido, methylureido, phenylureido), aphosphoramido group (preferably having from 1 to 30 carbon atoms, morepreferably from 1 to 20 carbon atoms, still more preferably from 1 to 12carbon atoms, e.g., diethylphosphoramido, phenylphosphoramido), ahydroxy group, a mercapto group, a halogen atom (e.g., fluorine,chlorine, bromine, iodine), a cyano group, a sulfo group, a carboxylgroup, a nitro group, a hydroxamic acid group, a sulfino group, ahydrazino group, an imino group and a heterocyclic group (preferablyhaving from 1 to 30 carbon atoms, more preferably from 1 to 20 carbonatoms; the hetero atom is, for example, a nitrogen atom, an oxygen atomor a sulfur atom; specific examples include imidazolyl, benzimidazolyl,benzoxazolyl, thiazolyl, benzothiazolyl, pyridyl, furyl, piperidyl andmorpholino). These substituents each may further be substituted.

Any of the substituents R₁₃ to R₁₈ may be combined to form a 5- or6-membered alicyclic, heterocyclic or aromatic ring, provided that R₁₆and R₁₇ are not combined to form an aromatic ring.

R₁₁ and R₁₂ each is preferably a substituted or unsubstituted alkylgroup having from 1 to 20 carbon atoms or an aryl group having from 6 to20 carbon atoms. R₁₁ and R₁₂ may combine with R₁₃ or R₁₄, respectively,to form a 5- or 6-membered alicyclic ring, for example, an indolinering, a tetrahydroquinoline ring or a Julolidine ring. R₁₁ and R₁₂ maybe combined to form a ring, for example, a pyrrolidine ring, apiperidine ring or a morpholine ring.

R₁₃, R₁₄ and R₁₅ each is preferably a hydrogen atom, a substituted orunsubstituted alkyl group having from 1 to 20 carbon atoms, a halogenatom, a hydroxy group, a substituted or unsubstituted alkoxy grouphaving from 1 to 20 carbon atoms, an unsubstituted amino group or asubstituted amino group having from 1 to 20 carbon atoms. Thesubstituted amino group is an alkylamino group, an arylamino group, anaromatic heterocyclic amino group, a sulfonamido group, a carbonamidogroup, a ureido group, a urethane group, a carbamoylamino group or asulfamoylamino group.

R₁₃, R₁₄ and R₁₅ each is more preferably a hydrogen atom, a substitutedor unsubstituted alkyl group having from 1 to 10 carbon atoms, asubstituted or unsubstituted alkoxy group having from 1 to 10 carbonatoms or a substituted amino group having from 1 to 10 carbon atoms. Thesubstituted amino group is an alkylamino group, an arylamino group, anaromatic heterocyclic amino group, a sulfonamido group, a carbonamidogroup, a ureido group, a urethane group, a carbamoylamino group or asulfamoylamino group.

R₁₆ and R₁₇ each is preferably a hydrogen atom, a halogen atom, asulfonamido group having from 1 to 30 carbon atoms, a carbonamido grouphaving from 1 to 30 carbon atoms or a ureido group having from 1 to 30carbon atoms. R₁₈ is preferably a hydrogen atom, a halogen atom, a cyanogroup, an alkyl group having from 1 to 30 carbon atoms, an aryl grouphaving from 6 to 30 carbon atoms, a heterocyclic group having from 2 to30 carbon atoms, a substituted carbonyl group having from 1 to 30 carbonatoms, a sulfamoyl group having from 0 to 30 carbon atoms, a sulfonamidogroup having from 1 to 30 carbon atoms, a carbonamido group having from1 to 30 carbon atoms or a ureido group having from 1 to 30 carbon atoms,more preferably a hydrogen atom, a halogen atom, a substituted carbonylgroup having from 1 to 30 carbon atoms or an amido group having from 1to 30 carbon atoms.

The preferred combination in formula (1) is described below.

In formula (1), preferred is the combination such that X₁₁ is an oxygenatom or N—R₁₉, R₁₉ is a substituted or unsubstituted alkyl group havingfrom 1 to 20 carbon atoms, a substituted carbonyl group having from 1 to20 carbon atoms or a substituted sulfonyl group having from 0 to 20carbon atoms, the substituent of the substituted carbonyl group is analiphatic group, an aryl group, a heterocyclic group, an alkoxy group oran aryloxy group, the substituent of the substituted sulfonyl group isan aliphatic group or aryl group, R₁₁ and R₁₂ each is an unsubstitutedor substituted alkyl group having from 1 to 20 carbon atoms or an arylgroup having from 6 to 20 carbon atoms and may combine with R₁₃ or R₁₄,respectively to form a ring (preferably a 5- or 6-membered alicyclicring), for example, an indoline ring, a tetrahydroquinoline ring or aJulolidine ring, or R₁₁ and R₁₂ may be combined with each other to forma ring, for example, a pyrrolidine ring, a piperidine ring or amorpholine ring, R₁₃, R₁₄ and R₁₅ each is a hydrogen atom, a substitutedor unsubstituted alkyl group having from 1 to 20 carbon atoms, a halogenatom or a substituted or unsubstituted alkoxy group having from 1 to 20carbon atoms, R₁₆ and R₁₇ each is a hydrogen atom, a halogen atom, asulfonylamino group having from 1 to 20 carbon atoms, an acylamino grouphaving from 2 to 20 carbon atoms or an ureido group having from 1 to 20carbon atoms, and R₁ is a hydrogen atom, a halogen atom, a cyano group,a substituted carbonyl group having from 1 to 20 carbon atoms, asulfamoyl group having from 0 to 20 carbon atoms, a sulfonylamino grouphaving from 1 to 20 carbon atoms, an acylamino group having from 1 to 20carbon atoms or a ureido group having from 1 to 20 carbon atoms.

Formula (2) is described below.

X₂₁ represents an oxygen-atom, a sulfur atom or N—R_(2b), preferably anoxygen atom or N—R_(2b). Examples and preferred range of R_(2b) are thesame as those of R₁₉ in formula (1). Y₂₁ represents an oxygen atom or asulfur atom, preferably an oxygen atom. Examples and preferred range ofR₂₁ to R₂₅ are the same as those of R₁₁ to R₁₅ in formula (1). Examplesof the substituent of R₂₆ to R₂₉ are the same as those of thesubstituent of R₁₃ to R₁₈ in formula (1). R₂₆ to R₂₉ each is preferablya hydrogen atom, a halogen atom, a substituted carbonyl group havingfrom 1 to 30 carbon atoms, an alkylamino group having from 1 to 30carbon atoms, an arylamino group having from 6 to 30 carbon atoms, asulfonylamino group having from 1 to 30 carbon atoms, an acylamino grouphaving from 2 to 30 carbon atoms, a ureido group having from 1 to 30carbon atoms, an alkoxycarbonylamino group having from 2 to 30 carbonatoms, an aryloxycarbonylamino group having from 7 to 30 carbon atoms, acarbamoylamino group having from 1 to 30 carbon atoms or asulfamoylamino group having from 1 to 30 carbon atoms. Examples of thesubstituent of the substituted carbonyl group include an alkyl group, anaryl group, an alkoxy group, an aryloxy group, an arylamino group and analkylamino group. R₂₆ to R₂₉ each is more preferably a hydrogen atom, anacylamino group having from 1 to 20 carbon atoms, a ureido group havingfrom 1 to 20 carbon atoms, an alkoxycarbonylamino group having from 2 to20 carbon atoms or an aryloxycarbonylamino group having from 7 to 20carbon atoms. Still more preferably, either one of R₂₆ and R₂₉ is anacylamino group having from 1 to 20 carbon atoms, a ureido group havingfrom 1 to 20 carbon atoms, an alkoxycarbonylamino group having from 2 to20 carbon atoms or an aryloxycarbonylamino group having from 7 to 20carbon atoms.

R_(2a) represents a hydrogen atom, an alkyl group, an alkenyl group, analkynyl group, an aryl group, a heterocyclic group, an unsubstitutedamino group, an acylamino group, a sulfonylamino group, a carbamoylaminogroup, a sulfamoylamino group, an alkoxycarbonylamino group, anaryloxycarbonylamino group, a phosphoramido group, an acyl group, acarbamoyl group, a sulfonyl group, a sulfamoyl group, a cyano group or ahalogen atom, preferably a hydrogen atom, a heterocyclic group, anunsubstituted amino group, an acylamino group, a sulfonylamino group, acarbamoylamino group, a sulfamoylamino group, an alkoxycarbonylaminogroup, an aryloxycarbonylamino group, an acyl group, a carbamoyl group,a sulfonyl group, a sulfamoyl group, a cyano group or a halogen atom,still more preferably a hydrogen atom, an acylamino group, asulfonylamino group, a carbamoylamino group, a sulfamoylamino group, analkoxycarbonylamino group, an aryloxycarbonylamino group, an acyl group,a carbamoyl group or a cyano group.

In formula (2), preferred is the combination such that X₂₁ is an oxygenatom or N—R_(2b), R_(2b) is a substituted or unsubstituted alkyl grouphaving from 1 to 20 carbon atoms, a substituted carbonyl group havingfrom 1 to 20 carbon atoms or a substituted sulfonyl group having from 0to 20 carbon atoms, the substituent of the substituted carbonyl group isan aliphatic group, an aryl group, a heterocyclic group, an alkoxy groupor an aryloxy group, the substituent of the substituted sulfonyl groupis an aliphatic group or an aryl group, Y₂₁ is an oxygen atom, R₂₁ andR₂₂ each is an unsubstituted or substituted alkyl group having from 1 to20 carbon atoms or an unsubstituted or substituted aryl group havingfrom 6 to 20 carbon atoms and may combine with R₂₃ or R₂₄, respectively,to form a ring (preferably, a 5- or 6-membered alicyclic ring), forexample, an indoline ring, a tetrahydroquinoline ring or a Julolidinering, or R₂₁ and R₂₂ may be combined with each other to form a ring, forexample, a pyrrolidine ring, a piperidine ring or a morpholine ring,R₂₃, R₂₄ and R₂₅ each is a hydrogen atom, a substituted or unsubstitutedalkyl group having from 1 to 20 carbon atoms or a substituted orunsubstituted alkoxy group having from 1 to 20 carbon atoms, R₂₆ to R₂₉each is a hydrogen atom, a sulfonylamino group having from 1 to 20carbon atoms, an acylamino group having from 2 to 20 carbon atoms, aureido group having from 1 to 20 carbon atoms, an alkoxycarbonylaminogroup having from 2 to 20 carbon atoms, an aryloxycarbonylamino grouphaving from 7 to 20 carbon atoms, a carbamoylamino group having from 1to 20 carbon atoms or a sulfamoylamino group having from 1 to 20 carbonatoms, and R_(2a) is a hydrogen atom, a heterocyclic group having from 2to 20 carbon atoms, an unsubstituted amino group, an acylamino grouphaving from 2 to 20 carbon atoms, a sulfonylamino group having from 1 to20 carbon toms, a carbamoylamino group having from 1 to 20 carbon atoms,a sulfamoylamino group having from 1 to 20 carbon atoms, analkoxycarbonylamino group having from 2 to 20 carbon atoms, anaryloxycarbonylamino group having from 7 to 20 carbon atoms, an acylgroup having from 2 to 20 carbon atoms, a carbamoyl group having from 1to 20 carbon atoms, a sulfonyl group having from 1 to 20 carbon atoms, asulfamoyl group having from 1 to 20 carbon atoms, a cyano group or ahalogen atom, provided that when X₂₁ is an oxygen atom and R_(2a) is ahydrogen atom, at least one of R₂₆ to R₂₉ is an unsubstituted orsubstituted amino group.

Formula (3) is described below.

X₃₁ represents an oxygen atom, a sulfur atom or N—R_(3b), preferably anoxygen atom or N—R_(3b). Examples and preferred range of R_(3b) are thesame as those of R₁₉ in formula (1). Z₃₁ represents NR₃₁R₃₂ or OG₃₁.Examples and preferred range of R₃₁ to R₃₅ are the same as those of R₁₁to R₁₅ in formula (1).

R₃₆ represents a hydrogen atom or a substituent.

Examples of the substituent are set forth below, however, the presentinvention is by no means limited thereto:

an alkyl group preferably having from 1 to 20 carbon atoms, morepreferably from 1 to 12 carbon atoms, still more preferably from 1 to 8carbon atoms, such as methyl, ethyl, iso-propyl, tert-butyl, n-octyl,n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl and cyclohexyl;

an alkenyl group preferably having from 2 to 20 carbon atoms, morepreferably from 2 to 12 carbon atoms, still more preferably from 2 to 8carbon atoms, such as vinyl, allyl, 2-butenyl and 3-pentenyl;

an alkynyl group preferably having from 2 to 20 carbon atoms, morepreferably from 2 to 12 carbon atoms, still more preferably from 2 to 8carbon atoms, such as propargyl and 3-pentynyl;

an aryl group preferably having from 6 to 30 carbon atoms, morepreferably from 6 to 20 carbon atoms, still more preferably from 6 to 12carbon atoms, such as phenyl, p-methylphenyl and naphthyl;

a substituted carbonyl group preferably having from 1 to 20 carbonatoms, more preferably from 1 to 16 carbon atoms, still more preferablyfrom 1 to 12 carbon atoms, such as acetyl, benzoyl, methoxycarbonyl,phenyloxycarbonyl, dimethylaminocarbonyl and phenylaminocarbonyl;

a substituted amino group preferably having from 1 to 20 carbon atoms,more preferably from 1 to 16 carbon atoms, still more preferably from 1to 12 carbon atoms, such as dimethylamino, methylcarbamoyl,ethylsulfonylamino, dimethylaminocarbonylamino and phthalimido;

a sulfonyl group preferably having from 1 to 20 carbon atoms, morepreferably from 1 to 16 carbon atoms, still more preferably from 1 to 12carbon atoms, such as mesyl and tosyl;

a heterocyclic group preferably having from 1 to 20 carbon atoms, morepreferably from 1 to 16 carbon atoms, still more preferably from 1 to 12carbon atoms (the hetero atom is, for example, oxygen, nitrogen orsulfur), such as imidazolyl, pyridyl, furyl, piperidyl, morpholino,benzoxazolyl and triazolyl;

an alkoxy group preferably having from 1 to 20 carbon atoms, morepreferably from 1 to 16 carbon atoms, still more preferably from 1 to 12carbon atoms, such as methoxy and benzyloxy;

an aryloxy group preferably having from 6 to 20 carbon atoms, morepreferably from 6 to 16 carbon atoms, still more preferably from 6 to 12carbon atoms, such as phenoxy and naphthyloxy;

a halogen atom, preferably a fluorine atom, a chlorine atom, a bromineatom or an iodine atom;

an alkylthio group preferably having from 1 to 20 carbon atoms, morepreferably from 1 to 16 carbon atoms, still more preferably from 1 to 12carbon atoms, such as methylthio;

an arylthio group preferably having from 6 to 20 carbon atoms, morepreferably from 6 to 16 carbon atoms, still more preferably from 6 to 12carbon atoms, such as phenylthio; and additionally

a sulfo group, a carboxyl group, a hydroxyl group, a thiol group and acyano group.

These substituents each may further be substituted.

R₃₆ is preferably a cyano group, a substituted or unsubstituted arylgroup, an aromatic heterocyclic group (for example, a substituted orunsubstituted benzazole group (e.g., benzoxazolyl) or a triazolylgroup), a substituted carbonyl group (for example, a phenylaminocarbonylgroup, a methoxycarbonyl group or t-butylcarbonyl group) or asubstituted sulfonyl group (for example, a methanesulfonyl group). R₃₆is more preferably a cyano group, a substituted or unsubstitutedbenzazole group (e.g., benzoxazolyl) or a substituted carbonyl group,still more preferably a substituted or unsubstituted benzazole group(e.g., benzoxazolyl) or a substituted carbonyl group.

G₃₁ represents a hydrogen atom, a substituent or a counter cation.Examples of the substituent include the substituents described above forR_(3b). The counter cation is not particularly limited, however,examples thereof include a metal cation (e.g., lithium ion, sodium ion,aluminum ion, europium ion) and a quaternary ammonium ion (preferablyhaving from 1 to 30 carbon atoms, more preferably from 1 to 20 carbonatoms, still more preferably from 1 to 10 carbon atoms, e.g.,tetrabutylammonium ion). The metal cation may have a ligand.

G₃₁ is preferably a hydrogen atom, a substituted or unsubstituted alkylgroup (preferably having from 1 to 30 carbon atoms, more preferably from1 to 20 carbon atoms, still more preferably from 1 to 10 carbon atoms,e.g., methyl, isopropyl, methoxyethoxymethyl), a substituted orunsubstituted aryl group (preferably having from 6 to 30 carbon atoms,more preferably from 6 to 20 carbon atoms, still more preferably from 6to 10 carbon atoms, e.g., phenyl, p-methoxyphenyl), an alkali metal ion,an alkaline earth metal ion, an aluminum ion, a zinc ion, a europiumion, a borate ion or a quaternary ammonium ion.

G₃₁ is more preferably a hydrogen atom, a substituted or unsubstitutedalkyl group, an alkali metal ion or a quaternary ammonium ion, stillmore preferably a hydrogen atom or a substituted or unsubstituted alkylgroup.

Formula (4) is described-below.

The compound represented by formula (4) is included in the compoundrepresented by formula (2).

The compound of formula (4) is preferably represented by the followingformula (5), (6), (7), (8) or (9):

In formula (5), preferred is the combination such that X₅₁ is an oxygenatom, a sulfur atom or N—R_(5b), R_(5b) is a hydrogen atom, asubstituted or unsubstituted alkyl group having from 1 to 20 carbonatoms, a substituted carbonyl group having from 1 to 20 carbon atoms ora substituted sulfonyl group having from 0 to 20 carbon atoms, R₅₁ andR₅₂ each is an unsubstituted or substituted alkyl group having from 1 to20 carbon atoms or an unsubstituted or substituted aryl group havingfrom 6 to 20 carbon atoms and may combine with R₅₃ or R₅₄, respectively,to form a ring (preferably a 5- or 6-membered alicyclic ring), forexample, an indoline ring, a tetrahydroquinoline ring or a Julolidinering, or R₅₁ and R₅₂ may be combined with each other to form a ring, forexample, a pyrrolidine ring, a piperidine ring or a morpholine ring,R₅₃, R₅₄ and R₅₅ each is a hydrogen atom, a substituted or unsubstitutedalkyl group having from 1 to 20 carbon atoms, a halogen atom, a hydroxygroup, a substituted or unsubstituted alkoxy group having from 1 to 20carbon atoms or an unsubstituted amino group or a substituted aminogroup having from 1 to 20 carbon atoms, R₅₆ to R₅₉ each is a hydrogentom, a halogen atom, a substituted carbonyl group having from 1 to 30carbon atoms, an alkylamino group having from 1 to 30 carbon atoms, anarylamino group having from 6 to 30 carbon atoms, a sulfonylamino grouphaving from 1 to 30 carbon atoms, an acylamino group having from 2 to 30carbon atoms, a ureido group having from 1 to 30 carbon atoms, analkoxycarbonylamino group having from 2 to 30 carbon atoms, anaryloxycarbonylamino group having from 7 to 30 carbon atoms, acarbamoylamino group having from 1 to 30 carbon atoms or asulfamoylamino group having from 0 to 30 carbon atoms, provided that atleast one of R₅₆ to R₅₉ is an unsubstituted or substituted amino group,and R_(5a) is a hydrogen atom or a cyano group.

More preferred is the combination such that X₅₁ is an oxygen atom orN—R_(5b), R_(5b) is a hydrogen atom, a substituted or unsubstitutedalkyl group having from 1 to 20 carbon atoms, a substituted carbonylgroup having from 1 to 20 carbon atoms or a substituted sulfonyl grouphaving from 0 to 20 carbon atoms, R₅₁ and R₅₂ each is an unsubstitutedor substituted alkyl group having from 1 to 20 carbon atoms or anunsubstituted or substituted aryl group having from 6 to 20 carbon atomsand may combine with R₅₃ or R₅₄, respectively, to form a ring(preferably a 5- or 6-memered alicyclic ring), for example, an indolering, a quinoline ring or a Julolidine ring, or R₅₁ and R₅₂ may becombined with each other to form a ring, for example, a pyrrolidinering, a piperidine ring or a morpholine ring, R₅₃, R₅₄ and R₅₅ each is ahydrogen atom, a substituted or unsubstituted alkyl group having from 1to 20 carbon atoms or a substituted or unsubstituted alkoxy group havingfrom 1 to 20 carbon atoms, R₅₆ to R₅₉ each is a hydrogen atom, asulfonylamino group having from 1 to 20 carbon atoms, an acylamino grouphaving from 2 to 20 carbon atoms, a ureido group having from 1 to 20carbon atoms, an alkoxycarbonylamino group having from 2 to 20 carbonatoms, an aryloxycarbonylamino group having from 7 to 20 carbon atoms, acarbamoylamino group having from 1 to 20 carbon atoms or asulfamoylamino group having from 1 to 20 carbon atoms, provided that atleast one of R₅₆ to R₅₉ is an acylamino group having from 2 to 20 carbonatoms, a sulfonylamino group having from 1 to 20 carbon atoms, a ureidogroup having from 1 to 20 carbon atoms, an alkoxycarbonylamino grouphaving from 2 to 20 carbon atoms, an aryloxycarbonylamino group havingfrom 7 to 20 carbon atoms, a carbamoylamino group having from 1 to 20carbon atoms or a sulfamoylamino group having from 0 to 20 carbon atoms,and R_(5a) is a hydrogen atom or a cyano group.

Still more preferred is the combination such that X₅₁ is an oxygen atomor N—R_(5b), R_(5b) is a substituted or unsubstituted alkyl group havingfrom 1 to 20 carbon atoms, R₅₁ and R₅₂ each is a substituted orunsubstituted alkyl group having from 1 to 12 carbon atoms or anunsubstituted or substituted aryl group having from 6 to 12 carbon atomsand may combine with R₅₃ or R₅₄, respectively, to form a ring or R₅₁ andR₅₂ may be combined with each other to form a ring, R₅₃, R₅₄ and R₅₅each is a hydrogen atom, a substituted or unsubstituted alkyl grouphaving from 1 to 12 carbon atoms or a substituted or unsubstitutedalkoxy group having from 1 to 12 carbon atoms, R₅₆ to R₅₉ each is ahydrogen atom, a sulfonylamino group having from 1 to 12 carbon atoms,an acylamino group having from 2 to 12 carbon atoms, a ureido grouphaving from 1 to 12 carbon atoms, an alkoxycarbonylamino group havingfrom 2 to 12 carbon atoms, an aryloxycarbonylamino group having from 7to 12 carbon atoms, preferably, either one of R₅₆ and R₅₉ is asulfonamido group having from 1 to 12 carbon atoms, a carbonamido grouphaving from 2 to 12 carbon atoms, a ureido group having from 1 to 12carbon atoms, an alkoxycarbonylamino group having from 2 to 12 carbonatoms or an aryloxycarbonylamino group having from 7 to 12 carbon atomsand the others each is a hydrogen atom, and R_(5a) is a hydrogen atom ora cyano group.

In formula (6), preferred is the combination such that X₆₁ is an oxygenatom or N—R_(6c), R_(6c) is a hydrogen atom, a substituted orunsubstituted alkyl group having from 1 to 20 carbon atoms, asubstituted carbonyl group having from 1 to 20 carbon atoms or asubstituted sulfonyl group having from 0 to 20 carbon atoms, R₆₁ and R₆₂each is an unsubstituted or substituted alkyl group having from 1 to 20carbon atoms or an unsubstituted or substituted aryl group having from 6to 20 carbon atoms and may combine with R₆₃ or R₆₄, respectively, toform a ring (preferably, a 5- or 6-membered alicyclic ring), forexample, an indoline ring, a tetrahydroquinoline ring or a Julolidinering or R₆₁ and R₆₂ may be combined with each other to form a ring, forexample, a pyrrolidine ring, a piperidine ring or a morpholine ring,R₆₃, R₆₄ and R₆₅ each is a hydrogen atom, a substituted or unsubstitutedalkyl group having from 1 to 20 carbon atoms, a halogen atom, a hydroxygroup, a substituted or unsubstituted alkoxy group having from 1 to 20carbon atoms, an unsubstituted amino group or a substituted amino grouphaving from 1 to 20 carbon atoms, R₆₆ to R₆₉ each is a hydrogen atom, ahalogen atom, a substituted carbonyl group having from 1 to 30 carbonatoms, an alkylamino group having from 1 to 30 carbon atoms, anarylamino group having from 1 to 30 carbon atoms, a sulfonylamino grouphaving from 1 to 30 carbon atoms, an acylamino group having from 2 to 30carbon atoms, a ureido group having from 1 to 30 carbon atoms, analkoxycarbonylamino group having from 2 to 30 carbon atoms, anaryloxycarbonylamino group having from 7 to 30 carbon atoms, acarbamoylamino group having from 1 to 30 carbon atoms or asulfamoylamino group having from 0 to 30 carbon atoms, and R_(6a) andR_(6b) each is a hydrogen atom, an alkyl group, an alkenyl group, analkynyl group, an aryl group, a heterocyclic group, an acyl group, analkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclicoxycarbonyl group, a sulfonyl group, a carbamoyl group or a sulfamoylgroup, provided that R_(6a) or R_(6b) is not combined with any one ofR₆₁ to R₆₉ to form a ring.

More preferred is the combination such that X₆₁ is an oxygen atom orN—R_(6c), R_(6c) is a hydrogen atom, a substituted or unsubstitutedalkyl group having from 1 to 20 carbon atoms, a substituted carbonylgroup having from 1 to 20 carbon atoms or a substituted sulfonyl grouphaving from 0 to 20 carbon atoms, R₆₁ and R₆₂ each is an unsubstitutedor substituted alkyl group having from 1 to 20 carbon atoms or anunsubstituted or substituted aryl group having from 6 to 20 carbon atomsand may combine with R₆₃ or R₆₄, respectively, to form a ring(preferably, a 5- or 6-membered alicyclic ring), for example, anindoline ring, a tetrahydroquinoline ring or a Julolidine ring or R₆₁and R₆₂ may be combined with each other to form a ring, for example, apyrrolidine ring, a piperidine ring or a morpholine ring, R₆₃, R₆₄ andR₆₅ each is a hydrogen atom, a substituted or unsubstituted alkyl grouphaving from 1 to 20 carbon atoms or a substituted or unsubstitutedalkoxy group having from 1 to 20 carbon atoms, R₆₆ to R₆₉ each is ahydrogen atom, a sulfonylamino group having from 1 to 20 carbon atoms,an acylamino group having from 2 to 20 carbon atoms, a ureido grouphaving from 1 to 20 carbon atoms, an alkoxycarbonylamino group havingfrom 2 to 20 carbon atoms, an aryloxycarbonylamino group having from 7to 20 carbon atoms, a carbamoylamino group having from 1 to 20 carbonatoms or a sulfamoylamino group having from 0 to 20 carbon atoms, andR_(6a) and R_(6b) each is a hydrogen atom, an acyl group having from 1to 20 carbon atoms, a sulfonyl group having from 1 to 20 carbon atoms, acarbamoyl group having from 1 to 20 carbon atoms, a Sulfamoyl grouphaving from 0 to 20 carbon atoms or an alkoxycarbonyl group having from2 to 20 carbon atoms, provided that R_(6a) or R_(6b) is not combinedwith any one of R₆₁ to R₆₉ to form a ring.

Still more preferred is the combination such that X₆₁ is an oxygen atomor N—R_(6c), R_(6c) is a substituted or unsubstituted alkyl group havingfrom 1 to 20 carbon atoms, R₆₁ and R₆₂ each is a substituted orunsubstituted alkyl group having from 1 to 12 carbon atoms or anunsubstituted or substituted aryl group having from 6 to 12 carbon atomsand may combine with R₆₃ or R₆₄, respectively, to form a ring or R₆₁ andR₂ may be combined with each other to form a ring, R₆₃, R₆₄ and R₆₅ eachis a hydrogen atom, a substituted or unsubstituted alkyl group havingfrom 1 to 12 carbon atoms or a substituted or unsubstituted alkoxy grouphaving from 1 to 12 carbon atoms, R₆₆ to R₆₉ each is a hydrogen atom, asulfonylamino group having from 1 to 12 carbon atoms, an acylamino grouphaving from 2 to 12 carbon atoms, a ureido group having from 1 to 12carbon atoms, an alkoxycarbonylamino group having from 2 to 12 carbonatoms or an aryloxycarbonylamino group having from 7 to 12 carbon atoms,and R_(6a) and R_(6b) each is a hydrogen atom, an acyl group having from1 to 12 carbon atoms, a sulfonyl group having from 1 to 12 carbon atoms,a carbamoyl group having from 1 to 12 carbon atoms, a sulfamoyl grouphaving from 0 to 12 carbon atoms or an alkoxycarbonyl group having from2 to 12 carbon atoms, provided that R_(6a) or R_(6b) is not combinedwith any one of R₆₁ to R₆₉ to form a ring.

In formula (7), preferred is the combination such that X₇₁ is an oxygenatom or N—R_(7b), R_(7b) is a hydrogen atom, a substituted orunsubstituted alkyl group having from 1 to 20 carbon atoms, asubstituted carbonyl group having from 1 to 20 carbon atoms or asubstituted sulfonyl group having from 0 to 20 carbon atoms, R₇₁ and R₇₂each is an unsubstituted or substituted alkyl group having from 1 to 20carbon atoms or an unsubstituted or substituted aryl group having from 6to 20 carbon atoms and may combine with R₇₃ or R₇₄, respectively, toform a ring (preferably, a 5- or 6-membered alicyclic ring), forexample, an indoline ring, a tetrahydroquinoline ring or a Julolidinering or R₇₁ and R₇₂ may be combined with each other to form a ring, forexample, a pyrrolidine ring, a piperidine ring or a morpholine ring,R₇₃, R₇₄ and R₇₅ each is a hydrogen atom, a substituted or unsubstitutedalkyl group having from 1 to 20 carbon atoms, a halogen atom, a hydroxygroup, a substituted or unsubstituted alkoxy group having from 1 to 20carbon atoms, an unsubstituted amino group or a substituted amino grouphaving from 1 to 20 carbon atoms, R₇₆ to R₇₉ each is a hydrogen atom, ahalogen atom, a substituted carbonyl group having from 1 to 30 carbonatoms, an alkylamino group having from 1 to 30 carbon atoms, anarylamino group having from 6 to 30 carbon atoms, a sulfonylamino grouphaving from 1 to 30 carbon atoms, an acylamino group having from 2 to 30carbon atoms, a ureido group having from 1 to 30 carbon atoms, analkoxycarbonylamino group having from 2 to 30 carbon atoms, anaryloxycarbonylamino group having from 7 to 30 carbon atoms, acarbamoylamino group having from 1 to 30 carbon atoms or asulfamoylamino group having from 0 to 30 carbon atoms, and R_(7a) is anaryl group, an alkoxy group, an aryloxy group, a heterocyclic oxy group,an unsubstituted or substituted amino group or a hydroxy group.

More preferred is the combination such that X₇₁ is an oxygen atom orN—R_(7b), R_(7b) is a hydrogen atom, a substituted or unsubstitutedalkyl group having from 1 to 20 carbon atoms, a substituted carbonylgroup having from 1 to 20 carbon atoms or a substituted sulfonyl grouphaving from 0 to 20 carbon atoms, R₇₁ and R₇₂ each is an unsubstitutedor substituted alkyl group having from 1 to 20 carbon atoms or anunsubstituted or substituted aryl group having from 6 to 20 carbon atomsand may combine with R₇₃ or R₇₄, respectively, to form a ring(preferably, a 5- or 6-membered alicyclic ring), for example, anindoline ring, a tetrahydroquinoline ring or a Julolidine ring or R₇₁and R₇₂ may be combined with each other to form a ring, for example, apyrrolidine ring, a piperidine ring or a morpholine ring, R₇₃, R₇₄ andR₇₅ each is a hydrogen atom, a substituted or unsubstituted alkyl grouphaving from 1 to 20 carbon atoms or a substituted or unsubstitutedalkoxy group having from 1 to 20 carbon atoms, R₇₆ to R₇₉ each is ahydrogen atom, a sulfonylamino group having from 1 to 20 carbon atoms,an acylamino group having from 2 to 20 carbon atoms, a ureido grouphaving from 1 to 20 carbon atoms, an alkoxycarbonylamino group havingfrom 2 to 20 carbon atoms, an aryloxycarbonylamino group having from 7to 20 carbon atoms, a carbamoylamino group having from 1 to 20 carbonatoms or a sulfamoylamino group having from 0 to 20 carbon atoms, andR_(7a) is an aryl group having from 6 to 20 carbon atoms, anunsubstituted amino group or a substituted amino group having from 1 to20 carbon atoms.

Still more preferred is the combination such that X₇₁ is an oxygen atomor N—R_(7b), R_(7b) is a substituted or unsubstituted alkyl group havingfrom 1 to 20 carbon atoms, R₇₁ and R₇₂ each is a substituted orunsubstituted alkyl group having from 1 to 12 carbon atoms or anunsubstituted or substituted aryl group having from 6 to 12 carbon atomsand may combine with R₇₃ or R₇₄, respectively, to form a ring or R₇₁ andR₇₂ may be combined with each other to form a ring, R₇₃, R₇₄ and R₇₅each is a hydrogen atom, a substituted or unsubstituted alkyl grouphaving from 1 to 12 carbon atoms or a substituted or unsubstitutedalkoxy group having from 1 to 12 carbon atoms, R₇₆ to R₇₉ each is ahydrogen atom, a sulfonylamino group having from 1 to 12 carbon atoms,an acylamino group having from 2 to 12 carbon atoms, a ureido grouphaving from 1 to 12 carbon atoms, an alkoxycarbonylamino group havingfrom 2 to 12 carbon atoms or an aryloxycarbonylamino group having from 7to 12 carbon atoms, and R_(7a) is a substituted or unsubstituted aminogroup having from 1 to 12 carbon atoms, particularly preferably asubstituted amino group in which the substituent is an alkyl grouphaving from 1 to 12 carbon atoms or an aryl group having from 6 to 12carbon atoms.

In formula (8), preferred is the combination such that X₈₁ is an oxygenatom, a sulfur atom or N—R_(8b), R_(8b) is a hydrogen atom, asubstituted or unsubstituted alkyl group having from 1 to 20 carbonatoms, a substituted carbonyl group having from 1 to 20 carbon atoms ora substituted sulfonyl group having from 0 to 20 carbon atoms, R₈₁ andR₈₂ each is an unsubstituted or substituted alkyl group having from 1 to20 carbon atoms or an unsubstituted or substituted aryl group havingfrom 6 to 20 carbon atoms and may combine with R₈₃ or R₈₄, respectively,to form a ring (preferably, a 5- or 6-membered alicyclic ring), forexample, an indoline ring, a tetrahydroquinoline ring or a Julolidinering or R₈₁ and R₈₂ may be combined with each other to form a ring, forexample, a pyrrolidine ring, a piperidine ring or a morpholine ring,R₈₃, R₈₄ and R₈₅ each is a hydrogen atom, a substituted or unsubstitutedalkyl group having from 1 to 20 carbon atoms, a halogen atom, a hydroxygroup, a substituted or unsubstituted alkoxy group having from 1 to 20carbon atoms, an unsubstituted amino group or a substituted amino grouphaving from 1 to 20 carbon atoms, R₈₆ to R₈₉ each is a hydrogen atom, ahalogen atom, a substituted carbonyl group having from 1 to 30 carbonatoms, an alkylamino group having from 1 to 30 carbon atoms, anarylamino group having from 6 to 30 carbon atoms, a sulfonylamino grouphaving from 1 to 30 carbon atoms, an acylamino group having from 2 to 30carbon atoms, a ureido group having from 1 to 30 carbon atoms, analkoxycarbonylamino group having from 2 to 30 carbon atoms, anaryloxycarbonylamino group having from 7 to 30 carbon atoms, acarbamoylamino group having from 1 to 30 carbon atoms or asulfamoylamino group having from 0 to 30 carbon atoms, and R_(8a) is analiphatic group, an aryl group, an alkoxy group, a substituted orunsubstituted amino group or a hydroxy group.

More preferred is the combination such that X₈₁ is an oxygen atom orN—R_(8b), R_(8b) is a hydrogen atom, a substituted or unsubstitutedalkyl group having from 1 to 20 carbon atoms, a substituted carbonylgroup having from 1 to 20 carbon atoms or a substituted sulfonyl grouphaving from 0 to 20 carbon atoms, R₈₁ and R₈₂ each is an unsubstitutedor substituted alkyl group having from 1 to 20 carbon atoms or anunsubstituted or substituted aryl group having from 6 to 20 carbon atomsand may combine with R₈₃ or R₈₄, respectively, to form a ring(preferably, a 5- or 6 membered alicyclic ring), for example, anindoline ring, a tetrahydroquinoline ring or a Julolidine ring or R₈₁and R₈₂ may be combined with each other to form a ring, for example, apyrrolidine ring, a piperidine ring or a morpholine ring, R₈₃, R₈₄ andR₈₅ each is a hydrogen atom, a substituted or unsubstituted alkyl grouphaving from 1 to 20 carbon atoms or a substituted or unsubstitutedalkoxy group having from 1 to 20 carbon atoms, R₈₆ to R₈₉ each is ahydrogen atom, a sulfonylamino group having from 1 to 20 carbon atoms,an acylamino group having from 2 to 20 carbon atoms, a ureido grouphaving from 1 to 20 carbon atoms, an alkoxycarbonylamino group havingfrom 2 to 20 carbon atoms, an aryloxycarbonylamino group having from 7to 20 carbon atoms, a carbamoylamino group having from 1 to 20 carbonatoms or a sulfamoylamino group having from 0 to 20 carbon atoms, andR_(8a) is an alkyl group having from 1 to 20 carbon atoms, an alkenylgroup, an alkynyl group, an aryl group having from 6 to 20 carbon atoms,an alkoxy group having from 1 to 20 carbon atoms, an unsubstituted aminogroup or a substituted amino group having from 1 to 20 carbon atoms.

Still more preferred is the combination such that X₈₁ is an oxygen atomor N—R_(8b), R_(8b) is a substituted or unsubstituted alkyl group havingfrom 1 to 20 carbon atoms, R₈₁ and R₈₂ each is a substituted orunsubstituted alkyl group having from 1 to 12 carbon atoms or anunsubstituted or substituted aryl group having from 6 to 12 carbon atomsand may combine with R₈₃ or R₈₄, respectively, to form a ring or R₈₁ andR₈₂ may be combined with each other to form a ring, R₈₃, R₈₄ and R₈₅each is a hydrogen atom, a substituted or unsubstituted alkyl grouphaving from 1 to 12 carbon atoms or a substituted or unsubstitutedalkoxy group having from 1 to 12 carbon atoms, R₈₆ to R₈₉ each is ahydrogen atom, a sulfonylamino group having from 1 to 12 carbon atoms,an acylamino group having from 2 to 12 carbon atoms, a ureido grouphaving from 1 to 12 carbon atoms, an alkoxycarbonylamino group havingfrom 2 to 12 carbon atoms or an aryloxycarbonylamino group having from 7to 12 carbon atoms, and R_(8a) is an alkyl group having from 1 to 12carbon atoms, an alkenyl group, an alkynyl group, an aryl group havingfrom 6 to 12 carbon atoms, a substituted or unsubstituted amino grouphaving from 1 to 12 carbon atoms, particularly preferably a substitutedamino group having from 1 to 12 carbon atoms in which the substituent isan alkyl group having from 1 to 12 carbon atoms or an aryl group havingfrom 6 to 12 carbon atoms.

The compounds represented by formulae (1) to (4) each may be a lowmolecular weight compound. A high molecular weight compound (preferablyhaving a weight-average molecular weight of from 1,000 to 5,000,000,more preferably from 5,000 to 2,000,000, still more preferably from10,000 to 1,000,000) where a residue represented by formula (1), (2),(3) or (4) is connected to the polymer main chain or a high molecularweight compound (preferably having a weight-average molecular weight offrom 1,000 to 5,000,000, more preferably from 5,000 to 2,000,000, stillmore preferably from 10,000 to 1,000,000) having a skeleton of formula(1), (2), (3) or (4) in the main chain may also be used. In the case ofa high molecular weight compound, the compound may be either ahomopolymer or a copolymer with another monomer.

The compounds represented by formulae (1) to (4) each is preferably alow molecular weight compound. For the sake of convenience, formulae (1)to (4) each is shown as a limiting structure but tautomers thereof mayalso be used.

Examples of the compounds represented by formulae (1) to (4) are setforth below, however, the present invention is by no means limitedthereto.

Examples of the Compound of Formula (1):

Examples of the Compounds of Formulae (2) and (4):

Examples of the Compound of Formula (3):

The synthesis method of the compounds of the present invention isdescribed below. The compounds of the present invention can besynthesized by various methods, however, in general, the compounds aresynthesized by a method of reacting an o-nitrosophenol with a naphtholderivative to cause cyclization and thereby synthesize the compound or amethod of oxidation coupling phenylenediamine or an aminophenol withphenol, naphthol or aniline described in items ([5] to [7] above asshown in the following Synthesis Examples.

Some synthesis examples of the compounds of the present invention aredescribed below.

SYNTHESIS EXAMPLE 1

Synthesis of Compound (1-3)

Compound (1-3) was synthesized by the method shown below.

More specifically, 5 ml of ethanol and 1 ml of water were added to 0.5 gof a phenol derivative (c) and the mixture was stirred at roomtemperature. Thereto, 0.5 g of potassium carbonate and 0.5 g of ammoniumpersulfate were added and the mixture was stirred at room temperaturefor one hour. After the completion of reaction, ethyl acetate and waterwas added to the reaction solution and the organic layer separated waswashed with water. The residue was crystallized in an ethylacetate/hexane system to obtain 0.17 g of crystals of Compound (1-3).The absorption spectrum determined in ethyl acetate revealed that λmaxwas 596 nm.

SYNTHESIS EXAMPLE 2

Synthesis of Compound (2-2):

A solution obtained by dissolving 6.03 g of 2-methylcarbamoyl-1-naphtholand 2-nitroso-5-diethylamino-phenol hydrochloride into 50 ml ofdimethylformamide was stirred under heating at 110° C. for 5 hours.After the completion of reaction, the temperature of the reactionsolution was lowered to room temperature, water was poured into thesolution, crystals precipitated was collected by filtration, washed withwater and dried, and the crude crystals obtained were purified through acolumn and then crystallized from chloroform-ethyl acetate. As a result,1.38 g of Compound (2-2) was obtained (absorption spectrum λmax: 570 nm(ClCH₂CH₂Cl)).

SYNTHESIS EXAMPLE 3

Synthesis of Compound (2-26)

In the same manner as in Synthesis Example 1, 611 mg of Compound (2-26)was obtained (absorption spectrum λmax: 576 nm).

SYNTHESIS EXAMPLE 4

In the same manner as in Synthesis Example 1, Compound (2-1) wasobtained (absorption spectrum λmax: 552 nm).

SYNTHESIS EXAMPLE 5

In the same manner as in Synthesis Example 1, Compound (2-27) wasobtained (absorption spectrum λmax: 582 nm).

SYNTHESIS EXAMPLE 6

In the same manner as in Synthesis Example 1, Compound (2-28) wasobtained (absorption spectrum λmax: 562 nm).

SYNTHESIS EXAMPLE 7

In the same manner as in Synthesis Example 1, Compound (2-42) wasobtained (absorption spectrum λmax: 551 nm).

SYNTHESIS EXAMPLE 8

Synthesis of Compound (2-44):

Compound (2-44) was synthesized by the method shown below.

More specifically, to 1.1 g of an amine derivative (b) and 1.0 g of aphenol derivative (a), 5 ml of ethanol and 1 ml of water were added andthe mixture was stirred at room temperature. Thereto, 1.05 g ofpotassium carbonate and 1.0 g of ammonium persulfate were added and themixture was stirred at room temperature for one hour. After thecompletion of reaction, ethyl acetate and water were added to thereaction solution and the organic layer separated was washed with 1Naqueous hydrochloric acid. The organic layer was dried over sodiumsulfate and concentrated to obtain crude crystals of Compound (2-44).The crude crystals were purified by the column chromatography(hexane/ethyl acetate system) to obtain 0.4 g of crystals of Compound(2-44). The absorption spectrum of Compound (2-44) determined in ethylacetate revealed that λmax was 548 nm and e was 57,000.

SYNTHESIS EXAMPLE 9

Synthesis of Compound (2-56):

According to the synthesis scheme shown below, 2.9 g of Compound (2-56)was synthesized in the same manner as in Synthesis Example of Compound(2-44). The absorption spectrum determined in dichloroethane revealedthat λmax was 524 nm.

SYNTHESIS EXAMPLE 10

Synthesis of Compound (2-58):

According to the synthesis scheme shown below, 0.5 g of Compound (2-58)was synthesized in the same manner as in Synthesis Example of Compound(2-44). The absorption spectrum determined in dichloroethane revealedthat λmax was 555 nm.

SYNTHESIS EXAMPLE 11

Synthesis of Compound (2-55)):

According to the synthesis scheme shown below, 3.1 g of Compound (2-55)was synthesized in the same manner as in Synthesis Example of Compound(2-44). The absorption spectrum determined in dichloroethane revealedthat λmax was 548 nm.

SYNTHESIS EXAMPLE 12

Synthesis of Compound (2-72):

According to the synthesis scheme shown below, 2.7 g of Compound (2-72)was synthesized in the same manner as in Synthesis Example of Compound(2-44). The absorption spectrum determined in dichloroethane revealedthat λmax was 546 nm.

SYNTHESIS EXAMPLE 13

Synthesis of Compound (3-1):

According to the synthesis scheme shown below, Compound (3-1) wassynthesized.

1 g of a phenyl ester (a-1) and 0.88 g of a phenylene-diamine derivative(a-2) were dissolved in a mixed solvent comprising 8 ml of ethylacetate, 2 ml of ethanol and 10 ml of water and thereto, 0.82 g ofpotassium carbonate and 0.8 g of ammonium persulfate were added,followed by stirring at room temperature for 30 minutes. The reactionsolution was diluted with 30 ml of ethyl acetate and 10 ml of water andthe organic layer separated was washed with aqueous hydrochloric acidand then with water. The organic layer was dried over sodium sulfate andthe organic solution was concentrated to obtain crude crystals. Thecrude crystals obtained were purified by the column chromatography(hexane/ethyl acetate system) to obtain 0.6 g of a cyclic azine dye(3-1). This dye had optical characteristics shown below.

λmax=442 (nm) (in ethyl acetate), ε=29900.

The EL device containing a cyclic azine-type dye of the presentinvention is described below. The method for forming an organic layer ofan EL device containing a cyclic azine-type dye of the present inventionis not particularly limited, however, a resistance heating evaporationmethod, an electron beam method, a sputtering method, a molecularlamination method and a coating method may be used and in view ofproperties and production, a resistance heating evaporation method and acoating method are preferred.

The electroluminescence device of the present invention is a devicecomprising a pair of electrodes of an anode and a cathode having formedtherebetween a light emitting layer or a plurality of organic compoundthin films including a light emitting layer. In addition to the lightemitting layer, a hole injecting layer, a hole transporting layer, anelectron injecting layer, an electron transporting layer and aprotective layer may also be provided. These layers each may haveanother function. For forming respective layers, various materials canbe used.

The anode feeds holes to the hole injecting layer, the hole transportinglayer or the light emitting layer and may use a metal, an alloy, a metaloxide, an electrically conductive compound or a mixture thereof butpreferably uses a material having a work function of 4 eV or more.Specific examples thereof include an electrically conductive metal oxidesuch as tin oxide, zinc oxide, indium oxide and indium tin oxide (ITO),a metal such as gold, silver, chromium and nickel, a mixture or laminateof the metal with the electrically conductive metal oxide, an inorganicelectrically conductive material such as copper iodide and coppersulfide, an organic electrically conductive material such aspolyaniline, polythiophene and polypyrrole, and a laminate of thematerial with ITO. Of these, an electrically conductive metal oxide ispreferred and in view of productivity, high electrical conductivity andtransparency, ITO is more preferred. The thickness of the anode may befreely decided depending on the material used, however, it is usually inthe range of preferably from 10 nm to 5 μm, more preferably from 50 nmto 1 tm, still more preferably from 100 to 500 nm.

The anode is usually used as a layer formed on a soda lime glass, analkali-free glass or a transparent resin substrate. In the case of usinga glass, the constructive material therefor is preferably an alkali-freeglass so as to reduce the ion dissolved out from the glass. In the caseof using a soda lime glass, the glass is preferably subjected to barriercoating with silica or the like. The thickness of the substrate is notparticularly limited as far as the substrate can maintain the mechanicalstrength, however, in the case of using a glass, it is usually 0.2 mm ormore, preferably 0.7 mm or more.

The anode may be prepared by various methods according to the materialused and for example, in the case of ITO, the film is formed by anelectron beam method, a sputtering method, a resistance heatingevaporation method, a chemical reaction method (sol-gel process) or amethod of coating an indium tin oxide dispersion.

By subjecting the anode to rinsing or other processings, the devicedriving voltage can be reduced or light emission efficiency can beincreased. For example, in the case of ITO, UV-ozone treatment andplasma treatment are effective.

The cathode feeds electrons to the electron injecting layer, theelectron transporting layer or the light emitting layer and is selectedby taking account of the adhesion to the layer adjacent to the negativeelectrode, such as an electron injecting layer, an electron transportinglayer and a light emitting layer, the ionization potential and thestability. As the material for the cathode, a metal, an alloy, a metalhalide, a metal oxide, an electrically conductive compound or a mixturethereof may be used and specific examples thereof include an alkalimetal (e.g., Li, Na, K) and a fluoride thereof, an alkaline earth metal(e.g., Mg, Ca) and a fluoride thereof, gold, silver, lead, aluminum, asodium-potassium alloy and a mixed metal thereof, a lithium-aluminumalloy and a mixed metal thereof, a magnesium-silver alloy and a mixedmetal thereof, and a rare earth metal such as indium and ytterbium. Ofthese, materials having a work function of 4 eV or less are preferred,and aluminum, a lithium-aluminum alloy and a mixed metal thereof and amagnesium-silver alloy and a mixed metal thereof are more preferred. Thecathode may be formed not only as a single layer of the above-describedcompound or mixture but also as a laminate structure including thecompound or mixture. The thickness of the cathode may be freely decideddepending on the material used, however, it is usually in the range ofpreferably from 10 nm to 5 μm, more preferably from 50 nm to 1 μm, stillmore preferably from 100 nm to 1 μm. The cathode may be prepared by anelectron beam method, a sputtering method, a resistance heatingevaporation method or a coating method, and a sole metal may bedeposited or two or more components may be simultaneously deposited.Furthermore, a plurality of metals may be simultaneously deposited toform an alloy electrode or an alloy previously prepared may bedeposited. The anode and the cathode each preferably has a low sheetresistance of hundreds of Ω/□ or less.

The material for the light emitting layer may be any as far as it canform a layer having a function of injecting holes from the anode, holeinjecting layer or hole transporting layer and at the same timeinjecting electrons from the cathode, electron injecting layer orelectron transporting layer upon application of an electric field, afunction of transferring charges injected, and a function of offering achance such that the hole and the electron recombine and emit light. Thelight emitting layer preferably contains a cyclic azine compound of thepresent invention but other light emitting materials may be used.Examples thereof include various metal complexes including metalcomplexes and rare earth complexes such as benzoxazole derivative,benzimidazole derivative, benzothiazole derivative, styrylbenzenederivative, polyphenyl derivative, diphenylbutadiene derivative,tetraphenyl-butadiene derivative, naphthalimide derivative, coumarinderivative, perylene derivative, perynone derivative, oxadiazolederivative, aldazine derivative, pyralidine derivative, cyclopentadienederivative, bisstyrylanthracene derivative, quinacridone derivative,pyrropyridine derivative, thiazolopyridine derivative, cyclopentadienederivative, styrylamine derivative, aromatic dimethylidyne compound and8-quinolinol derivative, and polymer compounds such as polythiophene,polyphenylene and polyphenylene-vinylene. The thickness of the lightemitting layer is not particularly limited, however, it is usually inthe range of preferably from 1 nm to 5 μm, more preferably from 5 nm to1 μm, still more preferably from 10 to 500 nm.

The method for forming the light emitting layer is not particularlylimited and a resistance heating evaporation method, an electron beammethod, a sputtering method, a molecular lamination method, a coatingmethod (e.g., spin coating, casting, dip coating) and an LB method areused. Of these, a resistance heating evaporation method and a coatingmethod are preferred.

The material for the hole injecting layer and the hole transportinglayer may be any as far as it has any one of a function of injectingholes from the anode, a function of transporting holes and a function ofblocking electrons injected from the cathode. Specific examples thereofinclude electrically conductive high molecular oligomers such ascarbazole derivative, triazole derivative, oxazole derivative,oxadiazole derivative, imidazole derivative, polyarylalkane derivative,pyrazoline derivative, pyrazolone derivative, phenylenediaminederivative, arylamine derivative, amino-substituted chalcone derivative,styrylanthracene derivative, fluorenone derivative, hydrazonederivative, stilbene derivative, silazane derivative, aromatic tertiaryamine compound, styrylamine compound, aromatic dimethylidyne-basedcompound, porphyrin-based compound, polysilane-based compound,poly(N-vinylcarbazole) derivative, aniline-based copolymer, thiopheneoligomer and polythiophene. The hole injecting layer and the holetransporting are not particularly limited on the thickness, however, thethickness is usually in the range of preferably from 1 nm to 5 μm, morepreferably from 5 nm to 1 μm, still more preferably from 10 to 500 nm.The hole injecting layer and the hole transporting layer each may have asingle layer structure comprising one or more of the above-describedmaterials or may have a multi-layer structure comprising a plurality oflayers which are the same or different in the composition.

The hole injecting layer and the hole transporting layer each is formedby a vacuum evaporation method, an LB method or a method of dissolvingor dispersing the above-described hole injecting and transporting agentin a solvent and coating the solution (e.g., spin coating, casting, dipcoating). In the case of the coating method, the material can bedissolved or dispersed together with a resin component. Examples of theresin component include polyvinyl chloride, polycarbonate, polystyrene,polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone,polyphenylene oxide, polybutadiene, poly(N-vinylcarbazole), hydrocarbonresin, ketone resin, phenoxy resin, polyamide resin, ethyl cellulose,vinyl acetate, ABS resin, polyurethane, melamine resin, unsaturatedpolyester resin, alkyd resin, epoxy resin and silicone resin.

The material for the electron injecting layer and the electrontransporting layer may be any as far as it has any one of a function ofinjecting electrons from the cathode, a function of transportingelectrons and a function of blocking holes injected from the anode.Specific examples thereof include heterocyclic tetracarboxylic acidanhydrides such as triazole derivative, oxazole derivative, oxadiazolederivative, fluorenone derivative, anthraquinodimethane derivative,anthrone derivative, diphenylquinone derivative, thiopyran dioxidederivative, carbidiimide derivative, fluorenylidenemethane derivative,distyryl-pyrazine derivative and naphthalene perylene, and various metalcomplexes such as metal complex of phthalocyanine derivative and8-quinolinol derivative, and metal complex containing metalphthalocyanine, benzoxazole or benzothiazole as a ligand. The electroninjecting layer and the electron transporting layer are not particularlylimited on the thickness, however, the thickness is usually in the rangeof preferably from 1 nm to 5 μm, more preferably from 5 nm to 1 μm,still more preferably from 10 to 500 nm. The electron injecting layerand the electron transporting layer each may have a single layerstructure comprising one or more of the above-described materials or mayhave a multi-layer structure comprising a plurality of layers which arethe same or different in the composition.

The electron injecting layer and the electron transporting layer each isformed by a vacuum evaporation method, an LB method or a method ofdissolving or dispersing the above-described electron injecting andtransporting agent in a solvent and coating the solution (e.g., spincoating, casting, dip coating). In the case of the coating method, thematerial can be dissolved or dispersed together with a resin component.Examples of the resin component include those described for the holeinjecting and transporting layer.

The material for the protective layer may any as far as it has afunction of preventing a substance which accelerates deterioration ofthe device, such as moisture and oxygen, from entering the device.Specific examples thereof include metals such as In, Sn, Pb, Au, Cu, Ag,Al, Ti and Ni, metal oxides such as MgO, SiO, SiO₂, Al₂O₃, GeO, NiO,CaO, BaO, Fe₂O₃, Y₂O₃ and TiO₂, metal fluorides such as MgF₂, LiF, AlF₃and CaF₂, polyethylene, polypropylene, polymethyl methacrylate,polyimide, polyurea, polytetrafluoroethylene,polychlorotrifluoroethylene, polydichlorodifluoroethylene, a copolymerof chlorotrifluoroethylene and dichlorodifluoroethylene, a copolymerobtained by copolymerizing a monomer mixture containingtetrafluoro-ethylene and at least one comonomer, a fluorine-containingcopolymer having a cyclic structure in the copolymer main chain, a waterabsorptive substance having a coefficient of water absorption of 1% ormore, and a moisture-proofing substance having a coefficient of waterabsorption of 0.1% or less.

The method for forming the protective layer is not particularly limitedand, for example, a vacuum evaporation method, a sputtering method, areactive sputtering method, an MBE (molecular beam epitaxy) method, acluster ion beam method, an ion plating method, a plasma polymerizationmethod (high frequency exciting ion plating method), a plasma CVDmethod, a laser CVD method, a thermal CVD method and a gas source CVDmethod may be used.

The compounds represented by formulae (1) to (4) of the presentinvention may be used, in addition to the use for organic EL devices,for photographic dyes, ink jet dyes, printing dyes, heat-sensitivetransfer recording dyes, color filter dyes, color conversion filter dyesor medical items.

The present invention is described in greater detail below, however, thepresent invention should not be construed as being limited thereto.

EXAMPLE 1

A glass plate in a size of 25 mm×25 mm×0.7 mm having formed thereon a150 nm-thick ITO film (manufactured by Tokyo Sanyo Shinku KK) was usedas a transparent substrate. This transparent substrate was etched andrinsed. Thereafter, a solution obtained by dissolving 40 mg ofpoly(N-vinylcarbazole), 12 mg of PBD(2-(4-biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole) and 0.5 mg ofa compound shown in Table 1 in 3 ml of 1,2-dichloroethane wasspin-coated on the rinsed ITO substrate. The organic thin film producedhad a thickness of about 120 nm. On the organic thin film, a patternedmask (mask having an emission area of 5 mm×5 mm) was provided. Then, inan evaporation apparatus, magnesium : silver (10:1) were co-deposited tohave a thickness of 50 nm and further silver was deposited to have athickness of 50 nm.

A dc constant voltage was applied to the EL device obtained to causelight emission using a source measure unit Model 2400 (manufactured byToyo Technica KK) and the luminance and emission wavelength thereof weredetermined by a luminance meter BM-8 (manufactured by Topcon KK) and aspectrum analyzer PMA-11 (manufactured by Hamamatsu Photonics KK),respectively. The results obtained are shown in Table 1.

TABLE 1 CIE Emission Driving Emission Chromaticity Device LuminanceVoltage Wavelength, Coordinates No. Compound (cd/m²) (V) λmax (nm) (x,y) Remarks Comparative Compound 101 A  70 16 595 (0.50, 0.50) Comparison102 B  25 18 603 (0.59, 0.40) ″ Compound of the Invention 103 2-1 100 15615 (0.62, 0.35) Invention 104 2-2 245 13 605 (0.60, 0.39) ″ 105 2-19200 15 615 (0.60, 0.37) ″ 106 2-26 168 15 620 (0.62, 0.36) ″ 107 2-28260 14 618 (0.61, 0.38) ″ 108 2-34 210 14 612 (0.60, 0.37) ″ 109 2-39280 14 610 (0.59, 0.37) ″ Comparative Compound A:

Comparative Compound B:

As apparent from the results in Table 1, in the case of devices usingthe compound of the present invention, low voltage driving and highluminance light emission could be attained as compared with the devicesusing a comparative compound even in the coating method where theemission luminance is usually low, and at the same time, red lightemission in high color purity was exhibited.

EXAMPLE 2

In the same manner as in Example 1, an ITO substrate was etched andrinsed and thereon TPD(N,N′-bis(3-methylphenyl)-N,N′-diphenylbenzidine), a compound shown inTable 2 and 2,5-bis(1-naphthyl)-1,3,4-oxadiazole were in sequencedeposited in a vacuum of from 10⁻⁵ to 10⁻⁶ Torr under the condition ofthe substrate temperature being room temperature to have a thickness ofabout 40 nm, about 20 nm and about 40 nm, respectively. Thereafter, acathode was deposited in the same manner as in Example 1 and the deviceswere evaluated. The results obtained are shown in

TABLE 2 CIE Emission Driving Emission Chromaticity Device LuminanceVoltage Wavelength, Coordinates No. Compound (cd/m²) (V) λmax (nm) (x,y)Remarks Comparative Compound 101 A 250 16 610 (0.54, 0.48) Comparison102 B 110 16 635 (0.64, 0.32) ″ Compound of the Invention 103 2-1 200 15640 (0.66, 0.32) Invention 104 2-2 310 13 635 (0.65, 0.33) ″ 106 2-26210 15 640 (0.66, 0.31) ″ 108 2-34 280 14 635 (0.64, 0.30) ″

As apparent from the results in Table 2, in the case of devices usingthe compound of the present invention, high luminance light emissioncould be attained as compared with the devices using a comparativecompound and at the same time, red light emission in high color puritywas exhibited.

EXAMPLE 3

In the same manner as in Example 1, an ITO substrate was etched andrinsed. On the rinsed substrate, TPD was deposited to have a thicknessof about 40 nm and then a compound shown in Table 3 and Alq(tris(8-hydroxy-quinolinato)aluminum) were co-deposited at a depositionrate of 0.04 Å/sec and 4 Å/sec, respectively, to have a thickness ofabout 60 nm. Thereafter, a cathode was deposited in the same manner asin Example 1 and the devices were evaluated. The results obtained areshown in Table 3.

TABLE 3 Emission CIE Emission Driving Wave- Chromaticity DeviceLuminance Voltage length, Coordinates Dark No. Compound (cd/m²) (V) λmax(nm) (x,y) Spot Remarks Comparative Compound 101 A 250 15 605 (0.51,0.48) Δ Comparison 102 B 150 17 635 (0.64, 0.33) x ″ Compound of theInvention 103 2-1 900 17 637 (0.65, 0.32) ∘ Invention 104 2-2 1050  14633 (0.64, 0.33) ∘ ″ 106 2-26 360 16 640 (0.66, 0.31) Δ ″ 108 2-34 76014 630 (0.60, 0.30) ∘ ″ *∘: Dark spots cannot be visually confirmed. Δ:Few dark spots. x: Many dark spots.

As apparent from the results in Table 3, in the case of devices usingthe compound of the present invention, high luminance light emissioncould be attained as compared with the devices using a comparativecompound also in the evaporation method and doped system, color puritywas high, red light emission excellent in the face state was exhibited,and durability was superior.

EXAMPLE 4

In the same manner as in Example 1, an ITO substrate was etched andrinsed. On the rinsed substrate, TPD was deposited to have a thicknessof about 40 nm and then Compound 2-2 was deposited to have a thicknessof about 60 nm. Thereafter, a cathode was deposited in the same manneras in Example 1.

As a result of evaluation, the device fabricated exhibited a luminanceof 120 cd/m² at 11 V. Furthermore, red light emission in high colorpurity such that λmax=630 nm and CIE chromaticity (x,y)=(0.67, 0.32) wasobserved. Thus, the compound of the present invention was verified to beeffective as an electron injecting and transporting agent and at thesame time, as an emitter.

EXAMPLE 5

In the same manner as in Example 1, an ITO substrate was etched andrinsed, and thereon, a solution obtained by dissolving 40 mg ofpoly(N-vinylcarbazole), 12 mg of 2,5-bis(1-naphthyl)-1,3,4-oxdiazole, 10mg of tetrapheyl-butadiene, 0.5 mg of DCM and 0.1 mg of Compound 2-1 ofthe present invention in 3 ml of 1,2-dichloroethane was spin-coated.Thereafter, a cathode was deposited in the same manner as in Example 1.

Then, a dc voltage was applied to the device obtained using the ITOelectrode as an anode and the Mg:Ag electrode as a cathode to examinethe light emission properties. As a result, white light emission(luminance: 1,420 cd/m²) at (x,y)=(0.34, 0.36) on the CIE chromaticitydiagram was obtained at 15V. Thus, the device was verified to beeffective for white light emission.

EXAMPLE 6

A glass plate in a size of 25 mm×25 mm×0.7 mm having formed thereon a150 nm-thick ITO film (manufactured by Tokyo Sanyo Shinku KK) was usedas a transparent substrate. This transparent substrate was etched andrinsed. Thereafter, a solution obtained by dissolving 40 mg ofpoly(N-vinylcarbazole), 12 mg of PBD(2-(4-biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole) and 1.0 mg ofa compound shown in Table 4 in 3 ml of 1,2-dichloroethane wasspin-coated on the rinsed ITO substrate. The organic thin film producedhad a thickness of about 120 nm. On the organic thin film, a patternedmask was provided. Then, in an evaporation apparatus, magnesium : silver(10:1) were co-deposited to have a thickness of 250 nm and furthersilver was deposited to have a thickness of 300 nm.

A dc constant voltage was applied to the EL device obtained to causelight emission using a source measure unit Model 2400 (manufactured byToyo Technica KK) and the luminance and emission wavelength thereof weredetermined by a luminance meter BM-8 (manufactured by Topcon KK) and aspectrum analyzer PMA-11 (manufactured by Hamamatsu Photonics KK),respectively. The results obtained are shown in Table 4.

TABLE 4 Emission CIE Emission Driving Wave- Chromaticity DeviceLuminance Voltage length, Coordinates Dark No. Compound (cd/m²) (V) λmax(nm) (x, y) Spot Remarks Comparative Compound 101 A 200 16 595 (0.50,0.50) Δ Comparison 102 B 110 16 590 (0.52, 0.47) x ″ Compound of theInvention 103 2-44 220 14 600 (0.57, 0.46) ∘ Invention 104 2-45 190 16595 (0.55, 0.50) Δ ″ 105 2-46 220 16 600 (0.58, 0.43) Δ ″ 106 2-48 23015 605 (0.53, 0.48) ∘ ″ 107 1-3 250 16 625 (0.61, 0.35) Δ ″ 108 1-7 19016 630 (0.62, 0.32) Δ ″ 109 2-56 260 15 630 (0.63, 0.31) ∘ ″ *∘: Darkspots cannot be visually confirmed. Δ: Few dark spots. x: Many darkspots. Comparative Compound A:

Comparative Compound B:

Using Nile red as a comparative compound, a maximum luminance of 110cd/m² was exhibited at 16 V, the λmax of light emission was 590 nm anddark spots were visually observed on the emission surface.

As apparent from the results in Table 4, in the case of devices usingthe compound of the present invention, low voltage driving and highluminance light emission could be attained as compared with the devicesusing a comparative compound even in the coating method where theemission luminance is usually low, and at the same time, red lightemission in high color purity was exhibited. Furthermore, the durabilitywas superior.

EXAMPLE 7

In the same manner as in Example 6, an ITO substrate was etched andrinsed and thereon TPD(N,N′-bis(3-methylphenyl)-N,N′-diphenylbenzidine), a compound shown inTable 5 and 2,5-bis(1-naphthyl)-1,3,4-oxadiazole were in sequencedeposited in a vacuum of from 10⁻⁵ to 10⁻⁶ Torr under the condition ofthe substrate temperature being room temperature to have a thickness ofabout 40 nm, about 20 nm and about 40 nm, respectively. Thereafter, acathode was deposited in the same manner as in Example 1 and the deviceswere evaluated. The results obtained are shown in Table 5.

TABLE 5 CIE Emission Driving Emission Chromaticity Device LuminanceVoltage Wavelength, Coordinates No. Compound (cd/m²) (V) λmax (nm) (x,y)Remarks Comparative Compound 201 A 250 16 610 (0.54, 0.48) Comparison202 B 110 16 635 (0.64, 0.32) ″ Compound of the Invention 203 2-56 30015 635 (0.65, 0.33) Invention 204 2-58 190 15 640 (0.66, 0.32) ″ 2062-55 220 16 625 (0.64, 0.32) ″ 208 2-72 250 16 630 (0.65, 0.33) ″

As apparent from the results in Table 5, in the devices using thecompound of the present invention, high luminance light emission couldbe attained as compared with the devices using a comparative compoundalso in the evaporation method and at the same time, red light emissionin high color purity was exhibited.

EXAMPLE 8

In the same manner as in Example 6, an ITO substrate was etched andrinsed. On the rinsed substrate, TPD was deposited to have a thicknessof about 40 nm and then a compound shown in Table 6 and Alq(tris(8-hydroxy-quinolinato)aluminum) were co-deposited at a depositionrate of 0.04 Å/sec and 4 Å/sec, respectively, to have a thickness ofabout 60 nm. Thereafter, a cathode was deposited in the same manner asin Example 6 and the devices were evaluated. The results obtained areshown in Table 6.

TABLE 6 Emission CIE Emission Driving Wave- Chromaticity DeviceLuminance Voltage length, Coordinates Dark No. Compound (cd/m²) (V) λmax(nm) (x,y) Spot Remarks Comparative Compound 301 A 250 15 605 (0.51,0.48) Δ Comparison 302 B 150 17 635 (0.64, 0.33) x ″ Compound of theInvention 303 2-56 900 16 637 (0.65, 0.32) ∘ Invention 304 2-58 1050  14633 (0.64, 0.33) ∘ ″ 306 2-55 360 16 640 (0.66, 0.31) Δ ″ 308 2-72 76014 630 (0.60, 0.30) ∘ ″ *∘: Dark spots cannot be visually confirmed. Δ:Few dark spots. x: Many dark spots.

As apparent from the results in Table 6, in the case of devices usingthe compound of the present invention, high luminance light emissioncould be attained as compared with the devices using a comparativecompound also in the evaporation method and doped system, color puritywas high, red light emission excellent in the face state was exhibited,and durability was superior.

EXAMPLE 9

In the same manner as in Example 6, an ITO substrate was etched andrinsed. On the rinsed substrate, TPD was deposited to have a thicknessof about 40 nm and then Compound 2-58 was deposited to have a thicknessof about 60 nm. Thereafter, a cathode was deposited in the same manneras in Example 6.

As a result of evaluation, the device fabricated exhibited a luminanceof 110 cd/m² at 12 V. Furthermore, red light emission in high colorpurity such that λmax=625 nm and CIE chromaticity (x,y)=(0.66, 0.32) wasobserved. Thus, the compound of the present invention was verified to beeffective as an electron injecting and transporting agent and at thesame time, as an emitter.

EXAMPLE 10

In the same manner as in Example 6, an ITO substrate was etched andrinsed, and thereon, a solution obtained by dissolving 40 mg ofpoly(N-vinylcarbazole), 12 mg of 2,5-bis(1-naphthyl)-1,3,4-oxadiazole,10 mg of tetraphenyl-butadiene, 0.5 mg of DCM and 0.1 mg of Compound2-58 of the present invention in 3 ml of 1,3-dichloroethane wasspin-coated. Thereafter, a cathode was deposited in the same manner asin Example 6.

Then, a dc voltage was applied to the device obtained using the ITOelectrode as an anode and the Mg:Ag electrode as a cathode to examinethe light emission properties. As a result, white light emission(luminance: 1,280 cd/m²) at (x,y)=(0.36, 0.35) on the CIE chromaticitydiagram was obtained at 16 V. Thus, the device was verified to beeffective for white light emission.

COMPARATIVE EXAMPLE

40 mg of polyvinylcarbazole, 12 mg of PBD(p-t-butyl-phenylbiphenyloxadiazole) and 1 mg of tetraphenylbutadienewere dissolved in 3 ml of dichloroethane and the solution obtained wasspin-coated on a rinsed ITO substrate. The organic thin film producedhad a thickness of about 120 nm. A patterned mask was provided on theorganic thin film. Then, in an evaporation apparatus, magnesium : silver(10:1) were co-deposited to have a thickness of 250 nm and then silverwas deposited thereon to have a thickness of 300 nm.

A dc constant voltage was applied to the EL device to cause lightemission using a source measure unit Model 2400 (manufactured by ToyoTechnica KK) and the luminance and emission wavelength thereof weredetermined by a luminance meter BM-8 (manufactured by Topcon KK) and aspectrum analyzer PMA-11 (manufactured by Hamamatsu Photonics KK),respectively. As a result, a maximum luminance of 280 cd/m² wasexhibited at 12 V and the λmax of light emission was 450 nm. The devicefabricated was left standing for 5 hours and then made to emit light.Then, dark spots were visually observed on the emission surface. Thegeneration of dark spots on the emission surface reveals that the deviceis deteriorated.

EXAMPLE 11

An EL device was fabricated in the same manner except for using thecyclic azine dye (3-1) synthesized above in place oftetraphenylbutadiene used in the Comparative Example, and evaluated. Asa result, light emission of λmax=480 nm was obtained and luminance of520 cd/m² was achieved at 14 V. No dark spot was visually observed onthe light emission surface.

EXAMPLE 12

An EL device was fabricated in the same manner except for using thecyclic azine dye (3-5) synthesized above in place oftetraphenylbutadiene used in the Comparative Example, and evaluated. Asa result, light emission of λmax=485 nm was obtained and luminance of435 cd/m² was achieved at 15 V. No dark spot was visually observed onthe light emission surface.

EXAMPLE 13

An EL device was fabricated in the same manner except for using thecyclic azine dye (3-13) synthesized above in place oftetraphenylbutadiene used in the Comparative Example, and evaluated. Asa result, light emission of λmax=465 nm was obtained and luminance of290 cd/m² was achieved at 16 V. No dark spot was visually observed onthe light emission surface.

It is apparent from the results in the Examples above that when a cyclicazine dye specified in the present invention is used, a blue-greenemissive EL device capable of emitting light at a wavelength in theblue-green area can be fabricated and the cyclic azine dye has excellentdurability.

While the invention has been described in detail and with reference tospecific embodiments thereof, it will be apparent to one skilled in theart that various changes and modifications can be made therein withoutdeparting from the spirit and scope thereof.

What is claimed is:
 1. An organic electroluminescence device comprising at least one organic thin film between electrodes, which contains at least one compound represented by the following formula (1):

wherein X₁₁ represents a sulfur atom or N—R₁₉, and R₁₁ to R₁₈ and R₁₉, which may be the same or different, each represents a hydrogen atom or a substituent, provided that R₁₆ and R₁₇ are not combined to form an aromatic ring.
 2. An organic electroluminescence device comprising a pair of electrodes having formed therebetween a light emitting layer or a plurality of organic compound thin films including a light emitting layer, wherein at least one layer is a layer comprising a polymer having dispersed therein a compound represented by formula (1):

wherein X₁₁ represents a sulfur atom or N—R₁₉, and R₁₁ to R₁₈ and R₁₉, which may be the same or different, each represents a hydrogen atom or a substituent, provided that R₁₆ and R₁₇ are not combined to form an aromatic ring.
 3. An organic electroluminescence device comprising a pair of electrodes having formed therebetween a light emitting layer or a plurality of organic compound thin films including a light emitting layer, wherein at least one layer is a layer formed by coating a compound represented by formula (1) or a material containing the compound:

wherein X₁₁ represents a sulfur atom or N—R₁₉, and R₁₁ to R₁₈ and R₁₉, which may be the same or different, each represents a hydrogen atom or a substituent, provided that R₁₆ and R₁₇ are not combined to form an aromatic ring. 